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1.
ZnSiO3 clinopyroxene stable above 3 GPa transforms to ilmenite at 10–12 GPa, which further decomposes into ZnO (rock salt) plus stishovite at 20–30 GPa. The enthalpy of the clinopyroxene-ilmenite transition was measured by high-temperature solution calorimetry, giving ΔH0=51.71 ±3.18 kJ/mol at 298 K. The heat capacities of clinopyroxene and ilmenite were measured by differential scanning calorimetry at 343–733 and 343–633 K, respectively. The C p of ilmenite is 3–5% smaller than that of clinopyroxene. The entropy of transition was calculated using the measured enthalpy and the free energy calculated from the phase equilibrium data. The enthalpy, entropy and volume changes of the pyroxene-ilmenite transition in ZnSiO3 are similar in magnitude to those in MgSiO3. The present thermochemical data are used to calculate the phase boundary of the ZnSiO3 clinopyroxene-ilmenite transition. The calculated boundary,
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2.
The relative stability of MgSiO3-ilmenite, MgSiO3-perovskite and (periclase+stishovite) assemblage phases as a function of the pressure is investigated with the periodic quantum mechanical ab initio HartreeFock program CRYSTAL. For the first time, the structure of MgSiO3-ilmenite is fully optimized. Basis set effects are explored. It turns out that relatively small basis sets reproduce correctly experimental geometries. However, larger basis sets (triple zeta quality, plus polarization d functions) are needed to yield significant thermochemical results. All contributions to the 0 K enthalpy are discussed. On the basis of the present highest level calculations, it appears that in the explored range of pressure (0P< 60=" gpa)=" the=" mineralogical=" assemblage=" periclase+stishovite=" has=" higher=" enthalpy=" than=">3-ilmenite or perovskite, and that ilmenite transforms to orthorhombic perovskite around to 29.4 GPa in good agreement with experimental data extrapolated down to 0 K.  相似文献   

3.
KAlSi3O8 sanidine dissociates into a mixture of K2Si4O9 wadeite, Al2SiO5 kyanite and SiO2 coesite, which further recombine into KAlSi3O8 hollandite with increasing pressure. Enthalpies of KAlSi3O8 sanidine and hollandite, K2Si4O9 wadeite and Al2SiO5 kyanite were measured by high-temperature solution calorimetry. Using the data, enthalpies of transitions at 298 K were obtained as 65.1 ± 7.4 kJ mol–1 for sanidine wadeite + kyanite + coesite and 99.3 ± 3.6 kJ mol–1 for wadeite + kyanite + coesite hollandite. The isobaric heat capacity of KAlSi3O8 hollandite was measured at 160–700 K by differential scanning calorimetry, and was also calculated using the Kieffer model. Combination of both the results yielded a heat-capacity equation of KAlSi3O8 hollandite above 298 K as Cp=3.896 × 102–1.823 × 103T–0.5–1.293 × 107T–2+1.631 × 109T–3 (Cp in J mol–1 K–1, T in K). The equilibrium transition boundaries were calculated using these new data on the transition enthalpies and heat capacity. The calculated transition boundaries are in general agreement with the phase relations experimentally determined previously. The calculated boundary for wadeite + kyanite + coesite hollandite intersects with the coesite–stishovite transition boundary, resulting in a stability field of the assemblage of wadeite + kyanite + stishovite below about 1273 K at about 8 GPa. Some phase–equilibrium experiments in the present study confirmed that sanidine transforms directly to wadeite + kyanite + coesite at 1373 K at about 6.3 GPa, without an intervening stability field of KAlSiO4 kalsilite + coesite which was previously suggested. The transition boundaries in KAlSi3O8 determined in this study put some constraints on the stability range of KAlSi3O8 hollandite in the mantle and that of sanidine inclusions in kimberlitic diamonds.  相似文献   

4.
Single crystal X-ray diffraction study of MgSiO3 perovskite has been completed from 77 to 400 K. The thermal expansion coefficient between 298 and 381 K is 2.2(8) × 10-5 K-1. Above 400 K, the single crystal becomes so multiply twinned that the cell parameters can no longer be determined.From 77 to 298 K, MgSiO3 perovskite has an average thermal expansion coefficient of 1.45(9) × 10-5 K-1, which is consistent with theoretical models and perovskite systematics. The thermal expansion is anisotropic; the a axis shows the most expansion in this temperature range (a = 8.4(9) × 10-6 K-1) followed by c(c = 5.9(5) × 10-6 K-1) and then by b, which shows no significant change in this temperature range. In addition, the distortion (i.e., the tilting of the [SiO6] octahedra) decreases with increasing temperature. We conclude that the behavior of MgSiO3 perovskite with temperature mirrors its behavior under compression.  相似文献   

5.
The mineral paragonite, NaAl2[AlSi3O10 (OH)]2, has been synthesized on its own composition starting from a variety of different materials. Indexed powder data and refined cell parameters are given for both the 1M and 2M1 polymorphs obtained. The upper stability limit of paragonite is marked by its breakdown to albite + corundum + vapour. The univariant equilibria pertaining to this reaction have been established by reversing the reaction at six different pressures, the equilibrium curve running through the following intervals: 1 kb: 530°–550° C 2 kb: 555°–575° C 3 kb: 580°–600° C 5kb: 625°–640° C 6 kb: 620°–650° C 7 kb: 650°–670° C.Comparison with the upper stability limit of muscovite (Velde, 1966) shows that paragonite has a notably lower thermal stability thus explaining the field observation that paragonite is absent in many higher grade metamorphic rocks in which muscovite is still stable.The enthalpy and entropy of the paragonite breakdown reaction have been estimated. Since intermediate albites of varying structural states are in equilibrium with paragonite, corundum and H2O along the univariant equilibrium curve, two sets of data pertaining to the entropy of paragonite (S 298 0 ) as well as the enthalpy ( H f,298 0 ) and Gibbs free energy ( G f,298 0 ) of its formation were computed, assuming (1) high albite and (2) low albite as the equilibrium phase. The values are: (1) (2) S 298 0 67.8±3.9 cal deg–1 gfw–1 63.7±3.9 cal deg–1 gfw–1 H f,298 0 –1417.9±2.7 kcal gfw–1 –1420.2±2.6 kcal gfw–1 G f,298 0 –1327.4±4.0 kcal gfw–1 –1328.5±4.0 kcal gfw–1.Adapted from a part of the author's Habilitationsschrift accepted by the Ruhr University, Bochum (Chatterjee, 1968).  相似文献   

6.
The Mogan and Fataga formations on the island of Gran Canaria, Canary Islands, represent a sequence of approximately 30 intercalated pyroclastic and lava flows (total volume about 500 km3 dense-rock equivalent) including subalkaline rhyolitic, peralkaline rhyolitic and trachytic pyroclastic flows, nepheline trachyte lavas and a small volume of alkali basaltic lavas and tephra deposits. The eruption of the intermediate to silicic rocks of the Mogan and Fataga formations follows the roughly 4 Ma duration of basaltic shield volcanism. The most common assemblage in the evolved (Mogan and Fataga) rocks is anorthoclase+ edenitic amphibole+ilmenite+magnetite±augite±hypersthene +apatite+pyrrhotite. A few flows also contain plagioclase, biotite, or sphene. Coexisting Fe-Ti oxides yield equilibrium temperatures between 835 and 930° C and log between –11.2 and –12.6. The lowermost pyroclastic flow of the Mogan formation is zoned from a rhyolitic base (848° C) to a basaltic top (931° C). Unit P1 has an oxygen isotope feldspar-magnetite temperature (850° C) very close to its Fe-Ti oxide temperature. One of the youngest Mogan flows is zoned from a comendite (836° C) at the base to a comenditic trachyte (899° C) at the top. The Fataga formation pyroclastic flows show only slight compositional zonation, and one flow has the same Fe-Ti oxide compositions at top and base.Calculations using the reaction 1/3 magnetite+SiO2 (melt)=ferrosilite+1/6 O2 indicate total pressures of 1–4 (±3) kb for six of the Mogan flows and one of the Fataga flows. For four of the pyroclastic flows, equilibria involving tremolite-SiO2-diopside-enstatite-H2O and phlogopite-SiO2-sanidine-enstatite-H2O imply water contents of 0.9 to 2.6 (±0.5) wt% and between 80 and 610 bars, which indicates that magma within the Tejeda reservoir was H2O-undersaturated throughout the entire history of Mogan to Fataga volcanism. The fluorine contents of amphibole, biotite, and apatite, and chlorine contents of apatite reveal thatf HF/ andf HCl/ high compared to most igneous rocks and are consistent with the peralkaline nature of most of the volcanics. Thef HCl estimate for one flow is 10–2 to 10–1 bars andf HF for six of the flows ranges from about 10–1 to 6 bars. Pyrrhotite compositions yield estimates for log between –1 and –3, log between –2 and 1.5, and log between 0.5 and 3, which fall in the range of most intermediate to silicic systems. The lack of a systematic trend with time for magma composition, Fe-Ti oxide temperatures, water contents, phenocryst abundances, and ferromagnesian phase composition indicate that the Tejeda magmatic system was open and kept at nearly the same conditions by the periodic addition of more primitive melts.The intensive thermodynamic parameters estimated from coexisting phenocryst equilibria are used to constrain the eruption dynamics based on solution of the conservation equations for a vapor plus pyroclast mixture. The estimates of magma reservoir temperature, pressure, and water concentration, when combined with a one-dimensional fluid dynamical model of a pyroclastic eruption, imply that the velocities of the ash flows at the vent exit were on the order of 100 to 200 m s–1, and the mass flow rates were about 107 kg s–1 for an assumed vent radius of 10 m.  相似文献   

7.
Structural parameters and thermodynamic properties of strontianite — witherite solid solutions have been studied by X-ray powder diffraction, heat flux Calvet calorimetry and cation-exchange equilibria technique. X-ray study of the synthetic samples have shown linear and quadratic (for c-parameter) composition dependencies of the lattice constants in the carbonate solid solution. The thermodynamic energy parameters demonstrate the non-ideal character of strontianite — witherite solid solutions. Enthalpies of solution of the samples have been measured in 2PbO*B2O3 at 973 K. The new data on the enthalpy of formation H f,298.15 0 of SrCO3 and BaCO3 were obtained: -1231.4±3.2 and -1209.9±5.8 kJ*mol-1 respectively. The enthalpy of mixing of the solid solution was found to be positive and asymmetric with maximum at XBa (carbonate)=0.35. The composition dependence of the enthalpy of mixing may be described by two — parametric Margules model equation: H mix=X BaX Sr[(4.40±3.91)X Ba+(28.13±3.91)X Sr] kJmol–1 Cation-exchange reactions between carbonates and aqueous SrCl2-BaCl2 supercritical solutions (fluids) were carried out at 973 and 1073 K and 2 kbar. Calculated Margules model parameters of the excess free energy are: for orthorhombic carbonate solid solutions W Sr=W Ba=11.51±0.40 kJmol–1 (973 K) and W Sr=W Ba=12.09±0.95 kJmol– (1073 K) for trigonal carbonate solid solutions W Sr=W Ba=13.55±0.40 kJmol– (1073 K).  相似文献   

8.
The assemblage paragonite + quartz is encountered frequently in low- to medium-grade metamorphic rocks. With rising grade of metamorphism they react mutually to yield the condensed assemblage albite + Al2SiO5.The univariant curve pertaining to the equilibrium paragonite + quartz=albite + andalusite + H2O has been located experimentally. The reversed P H 2 O-T data are: 1 kb: 470–490° C 2 kb: 510–530° C 3 kb: 540–560° C 4 kb: 560–580° C 5 kb: 590–600° C The univariant curve pertaining to the equilibrium paragonite + quartz=albite + kyanite + H2O runs through the following P H 2 O-T-intervals: 5 kb: 570–625° C 6 kb: 600–630° C 7 kb: 620–640° C Thermodynamic calculations of S 298 0 , H f,298 0 and G f,298 0 of the phase paragonite from the experimental data presented above and those obtained from the equilibria of the reaction paragonite=albite + corundum + H2O (Chatterjee, 1970), agree within the limits of uncertainty. This prompts the idea that Zen's (1969) suggestion of a possible error of approximately 7 kcal in G f,298 0 of the Al2SiO5 polymorphs may in fact be due to an error of similar magnitude in G f,298 0 of corundum.A best estimate of S 298 0 , H f,298 0 and G f,298 0 of paragonite based on these considerations yield: S 298 0 : 67.61±3.9 cal deg–1 gfw–1 H f,298 0 : –1411.4±2.7 kcal gfw–1 G f,298 0 : –1320.9±4.0 kcal gfw–1 These numbers will be subject to change when better thermochemical data on corundum and albite are available.In medium-grade metamorphic rocks the assemblage paragonite + quartz is commonly found in stable coexistence with such other phases as muscovite, staurolite, andalusite, kyanite, but not with cordierite or sillimanite. However, the assemblage paragonite-sillimanite has been reported to be stable in the absence of quartz. All these petrologic observations can be explained on the basis of the stability data of the phases and phase assemblages concerned.  相似文献   

9.
Stability of titanian clinohumite: Experiments and thermodynamic analysis   总被引：2，自引：0，他引：2  
Reversed hydrothermal experiments on a natural titanoclinohumite [Ti-Cl; approximate formula Mg7.5FeTi0.5O16(OH)] show that it breaks down at 475°±11° C (3.5 kbar), 620°±11° C (14 kbar) and 675°±8° C (21 kbar) to the assemblage olivine +ilmenite+vapor. An internal-consistency analysis of the data yields r G s /0 (298 K, 1 bar)=36,760±3,326 cal (mole Ti-Cl)–1. r S s /0 (298 K, 1 bar)=34.14±5.91 cal deg–1(mole Ti-Cl)–1. Linear correlation coefficient r G–S 1.0. A solution model that accounts for TiO2-M(OH)2 and F-OH substitution shows that the results for our nearly F-free Ti-Cl are in reasonable agreement with the unreversed breakdown experiments of Mer-rill et al. (1972) on a F-bearing Ti-Cl.Because fluorine is necessary to stabilize Ti-Cl under mantle conditions, we suggest that Ti-Cl is much more likely to be a storage device for fluorine than for water in the mantle.  相似文献   

10.
High temperature oxide melt solution calorimetry was used to study the energy associated with dislocations in quartz by comparing undeformed and deformed single crystals of synthetic quartz. Samples were deformed at 698 K, 1000–1500 MPa at a strain rate of 10–5 sec–1. Two sets of calorimetric measurements were made: (i) using a Pt capsule as a container for powdered sample, and (ii) using pellets made from sample powder without any container. For the first set of measurements, the undeformed sample with a dislocation density of enthalpy is sum of heat content H 973-H 295 and enthalpy of solution in molten lead borate at 973 K of 39.22 ± 1.00 kJ mol–1, while the sample deformed in the dislocation creep regime with a dislocation density of 6 × 1010 to 1 × 1011 cm–2 gave an enthalpy of 38.59 ± 0.78 kJ mol–1. For the second set of measurements the measured enthalpy of the undeformed sample was 38.87 ± 0.31 kJ mol–1, and that of a deformed sample with a dislocation density of 3 × 1010 to 1 × 1011 cm–2 was 38.24 ± 0.58 kJ mol–1.The present study and previous theoretical calculations and estimates are consistent and suggest that the energy associated with dislocations in quartz is 0.6 ± 0.6 kJ mol–1 for a dislocation density of 1011 cm–2; a precise value is difficult to determine because of the overlapping errors. These results indicate that for geologically realistic dislocation densities, the maximum excess energy due to dislocations would be 0.5 kJ mol–1 for most minerals; the exact value would depend on the Burgers vector as well as the shear modulus.  相似文献   

11.
The role of phase transformations in a mantle of pyrolite composition is reviewed in the light of recent experimental data. The pyroxene component of pyrolite transforms to the garnet structure at 300–350 km whilst olivine transforms to beta-Mg2SiO4 near 400 km. Between about 500 and 550 km, beta-Mg2SiO4 probably transforms to a partially inverse spinel structure whilst the CaSiO3 component of the complex garnet solid solution exsolves and transforms to the perovskite structure. The major seismic discontinuity near 650–700 km is probably caused by disproportionation of Mg2SiO4 spinel into periclase plus stishovite. At a slightly greater depth, the remaining magnesian garnet transforms to the corundum or ilmenite structure. Finally, at a depth probably in the vicinity of 800–1000 km, the (Mg,Fe)SiO3 component of the ilmenite phase transforms to a perovskite structure whilst stishovite and some of the periclase recombine to form perovskite also. The mineral assemblage so formed is about 4% denser than mixed oxides (MgO + FeO + A12O3 + CaO + stishovite) isochemical with pyrolite. The above sequence of phase transformations in pyrolite provides a satisfactory general explanation of the elastic properties and density distribution in the mantle. In particular, there is no evidence requiring an increase of FeO/(FeO + MgO) ratio with depth.The depths at which major phase transformations occur in subducted lithosphere differ from those in ‘normal’ mantle. These differences are caused by two factors: (1) Temperatures within sinking plates are much lower than in surrounding mantle to depths of 700 km or more. (2) Irreversible chemical differentiation of pyrolite occurs at oceanic ridges. Lithosphere plates so formed consist of a layer of basaltic rocks underlain successively by layers of harzburgite, lherzolite, and pyrolite slightly depleted in highly incompatible elements (e.g. La, Ba, Rb, U). The phase-transformation behaviour of the first three of these layers differs from that of pyrolite.The effects of these and other factors connected with phase transformations on the dynamics of plate subsidence are discussed. It appears quite likely that plates penetrate the 650–700 km discontinuity, largely because the slope of the spinel disproportionation is probably positive, not negative as generally supposed. The former basaltic oceanic crust probably sinks deeply into the lower mantle, whilst the former harzburgite component of the plate may collect above the perovskite transition boundary. Phase transformations may thus serve as a kind of filter, leading to increased and irreversible mantle heterogeneity with time.The possible roles of phase transformations in causing deep-focus earthquakes and introducing water into the mantle in subduction zones are also briefly discussed.  相似文献   

12.
Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO4 solutions. Single-crystal XRD refinement with R1=0.0232 for the unique observed reflections (|Fo| > 4F) and wR2=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, Vo=160.11(4) cm3, and fractional positions for all atoms except the H in the H3O groups. The chemical composition of this sample is described by the formula (H3O)0.91Fe2.91(SO4)2[(OH)5.64(H2O)0.18]. The enthalpy of formation (Hof) is –3694.5 ± 4.6 kJ mol–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H2O, and -MgSO4. The entropy at standard temperature and pressure (So) is 438.9±0.7 J mol–1 K–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (Cp) data between 273 and 400 K were fitted to a Maier-Kelley polynomial Cp(T in K)=280.6 + 0.6149T–3199700T–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol–1. Speciation and activity calculations for Fe(III)–SO4 solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the Cp data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in Cp, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H3O)Fe3(SO4)2(OH)6 was estimated: Gof= –3226.4 ± 4.6 kJ mol–1, Hof=–3770.2 ± 4.6 kJ mol–1, So=448.2 ± 0.7 J mol–1 K–1, Cp (T in K)=287.2 + 0.6281T–3286000T–2 (between 273 and 400 K).  相似文献   

13.
Glassy orthopyroxene granodiorite-tonalite (named pincinite after type locality) was described from basaltic lapilli tuffs of the Pliocene maar near Pinciná village in the Slovakian part of the Pannonian Basin. Two pincinite types exhibit a qualitatively similar mineral composition (quartz, An20–55 plagioclase, intergranular silicic glass with orthopyroxene and ilmenite, ±K-feldspar), but strongly different redox potential and formation PT conditions. Peraluminous pincinite is reduced (6–7% of total iron as Fe3+ in corundum-normative intergranular dacitic glass) and contains ilmenite with 8–10 mol% Fe2O3 and orthopyroxene dominated by ferrosilite. High-density (up to 0.85 g/cm3) primary CO2 inclusions with minor H2, CH4, H2S, CO and N2 (<2 mol% total) are present in Qtz and Plg. Equilibrium PT conditions inferred from the intergranular Opx–Ilm–Glass assemblage and fluid density correspond to 1,170±50°C, 5.6±0.4 kbar, respectively. Metaluminous pincinite is more oxidised (25–27% of total iron as Fe3+ in diopside-normative intergranular glass of rhyolite–trachyte–dacite composition) and contains Fe2O3-rich ilmenite (17–29 mol%) associated with enstatite. Fluid inclusions are composed of CO2–H2O mixtures with up to 38 mol% H2O. Raman spectroscopy revealed H2S along with dominant CO2 in the carbonic phase. Equilibrium PT parameters for the intergranular Opx–Ilm–Glass assemblage correspond to 740±15°C, 2.8±0.1 kbar, respectively. Reducing gas species (<2 mol% total) in the CO2-inclusions of the peraluminous pincinite resulted from hydrogen diffusion due to fH2 gradient imposed during decrease of redox potential from the log fO2 values near QFM during Qtz + Plg growth, to QFM-2 incidental to the superimposed Opx + Ilm assemblage in the intergranular melt. The decrease in oxygen fugacity was recorded also in the metaluminous pincinite, where log fO2 values changed from ~QFM + 2.6 to QFM + 0.4, but hydrogen diffusion did not occur. Absence of OH-bearing minerals, major and trace element abundances (e.g. REE 300–320, Nb 55–57, Th 4–31, Zr 240–300 ppm, FeOtot/MgO up to 11), and Sr–O isotope ratios in the pincinites are diagnostic of high-temperature anorogenic magmas originated by dehydration melting of biotite in quartz-feldspathoid crust (87Sr/86Sr>0.705–0.706, 18O>9 V-SMOW) around alkali basalt reservoir in depths between 17 and 20 km, and around late stage derivatives of the basalt fractionation, intruding the crust up to depths of 10–11 km. Low water activity in the pincinite parental melt was caused by CO2-flux from the Tertiary basaltic reservoirs and intrusions. The anatexis leads to generation of a melt-depleted granulitic crust beneath the Pannonian Basin, and the pincinites are interpreted as equivalents of igneous charnockites and enderbites quenched at temperatures above solidus and unaffected by sub-solidus re-equilibration and metamorphic overprint.  相似文献   

14.
Calcareous hornfelses and marbles all contain calcite+K-feldspar+quartz+sphene±diopside±plagioclase ±scapolite±clinozoisite. In addition, rocks on one side of a fault contain combinations of biotite, amphibole, and muscovite while those on the other side contain combinations of grossular, wollastonite, and axinite. At bars, mineral-fluid equilibria in biotite and amphibole-bearing rocks record T= 440° C and garnet-bearing rocks record T=540° C and Conventional volumetric fluid-rock ratios were calculated using measured progress of prograde decarbonation reactions and the conditions of metamorphism: marbles, 0–0.4; amphibole-bearing hornfelses, 1.0–1.4; garnet-bearing hornfelses, 2.8–6.7. Decarbonation reactions were driven by pervasive infiltration of rock by reactive aqueous fluids. Differences in fluid-rock ratio between interbedded marble and hornfels and lack of correlation between fluid-rock ratio and whole-rock Cl-content, however, argue for channelized fluid flow along lithologic layers. A new analysis of reaction progress allows estimation of time-integrated fluxes for a specified temperature gradient along the direction of flow. Results are: marbles, 0–0.1×105 cm3/cm2; amphibole-bearing hornfelses, 0.8–1.3×105 cm3/cm2; garnet-bearing hornfelses, 1.2–2.5 × 105 cm3/cm2. Fluid flowed from regions of low to regions of high temperature. Using a simple thermal model for the area, the duration of contact metamorphism was estimated as 105 years. Assuming the time of fluid flow was the same as the duration of the thermal event, the first measurements of average metamorphic fluxes (q) and permeabilities (k) are: average marbles, q=0–0.3×10–8 cm/s and k =2×10–6 darcy; hornfels, q=3–8×10–8 cm/s and k =20–53×10–6 darcy. Estimated premeabilities are within the range of values measured for metamorphic rocks in the laboratory. Fluxes, permeabilities, and whole-system fluidrock ratios are similar to those estimated for the Skaergaard hydrothermal system by Norton and Taylor (1979).  相似文献   

15.
The behaviour of synthetic Mg-ferrite (MgFe2O4) has been investigated at high pressure (in situ high-pressure synchrotron radiation powder diffraction at ESRF) and at high temperature (in situ high-temperature X-ray powder diffraction) conditions. The elastic properties determined by the third-order Birch–Murnaghan equation of state result in K0=181.5(± 1.3) GPa, K=6.32(± 0.14) and K= –0.0638 GPa–1. The symmetry-independent coordinate of oxygen does not show significant sensitivity to pressure, and the structure shrinking is mainly attributable to the shortening of the cell edge (homogeneous strain). The lattice parameter thermal expansion is described by a0+a1*(T–298)+a2/(T–298)2, where a0=9.1(1) 10–6 K–1, a1=4.9(2) 10–9 K–2 and a2= 5.1(5) 10–2 K. The high-temperature cation-ordering reaction which MgFe-spinel undergoes has been interpreted by the ONeill model, whose parameters are = 22.2(± 1.8) kJ mol–1 and =–17.6(± 1.2) kJ mol–1. The elastic and thermal properties measured have then been used to model the phase diagram of MgFe2O4, which shows that the high-pressure transition from spinel to orthorombic CaMn2O4-like structure at T < 1700 K is preceded by a decomposition into MgO and Fe2O3.  相似文献   

16.
The low-temperature heat capacity of -Mg2PO4OH was measured between 10 and 400 K by adiabatic calorimetry. No phase transition was observed over this temperature range. A relative enthalpy increment of 22,119 J mol–1 and an absolute entropy value of 127.13±0.25 J mol–1 K–1 at 298.15 K are derived from the results. The low-temperature heat-capacity data are compared with the DSC data obtained from 143 K to 775 K and show marginal differences in the common temperature range. The latter data are fitted by the polynomial
which allows extrapolation to high temperatures.Software information: WINDOWS operating system, WORD word processing, SigmaPlot diagrams exported in tiff format.  相似文献   

17.
Values of silica activity have been calculated for Bushveld rocks from an extension of the mafic layered sequence north of the town of Bethal in the south-eastern Transvaal as well as the Roossenekal area in the eastern limb of the Complex. The samples examined contain the coexisting assemblage olivine, Ca-poor pyroxene, Ca-rich pyroxene and plagioclase. This enabled silica activities to be calculated from the following reactions: (Mg, Fe)2SiO4+SiO22(Mg, Fe)SiO3, CaAl2SiO6+SiO2CaAl2Si2O8. Parallel curves of increasing silica activity with fractionation were established 0.20 log units apart. This represented a pressure of emplacement for the top of the layered zone in the Bethal area of 2.72±0.79 kbars. A value of 1.47±0.62 kbars was obtained for the Roossenekal area. These values are equivalent to 9.1±2.6 km and 4.9±2.1 km respectively, the latter figure being consistent with the minimum thickness of 4550 m of felsite and granophyre originally overlying the layered sequence and still preserved in the area west of Roossenekal.  相似文献   

18.
We conducted melting experiments on a low-alkali tholeiite (SiO2 ~52 wt%, MgO ~6.5 wt%, CaO/Na2O~4.4, Al2O3/SiO2 ~0.33) under both H2O-undersaturated and H2O-saturated conditions to investigate the effect of H2O on the Ca–Na partitioning between plagioclase and melt. Experiments were performed in the temperature and pressure ranges of 1,000–1,300°C and 1–5 kbar, respectively, with varying H2O contents of 0–12wt%. Redox condition was 0–2 log unit above NNO (nickel–nickel oxide) buffer. Temperature-bulk H2O diagrams for the low-alkali tholeiite are constructed at 1, 2, and 5 kbar, and compositions of near-liquidus plagioclase and coexisting melt are determined. To exclude the effect of melt composition (CaO/Na2O and Al2O3/SiO2 ratios) on plagioclase composition and to reveal the effect of H2O on An (=100×Ca/(Ca+Na)) content and (=(Ca/Na)pl/(Ca/Na)melt), we focused on the composition of near-liquidus plagioclases which crystallized from melts with nearly constant CaO/Na2O and Al2O3/SiO2 ratios. Our experimental results show that, at each experimental pressure, An content of the near-liquidus plagioclase and the KDCa-Na almost linearly increases as H2O content in melt increases. Each of the An content and the variations in a low-alkali tholeiitic system (CaO/Na2O~4.0–4.5, Al2O3/SiO2 ~0.27–0.33) can be described by one equation using temperature, pressure, and melt H2O content as parameters. An content and of liquidus plagioclase increases with increasing melt H2O and with decreasing pressure, elucidating that nearly H2O-saturated conditions of 2–3 kbar is optimal for the crystallization of the most An-rich plagioclase (>An88). We suggest this pressure condition of 2–3 kbar, corresponding to depth of 7–11 km, plays an important role for the origin of An-rich plagioclase in H2O-rich low-alkali tholeiite. At pressures more than ca. 4 kbar, crystallization of liquidus Ca-rich clinopyroxene decreases the CaO/Na2O ratio of liquid, thus prohibiting the crystallization of high-An plagioclase from hydrous tholeiite.  相似文献   

19.
Heats of mixing of synthetic C2/m fluortremolite-fluoredenite amphiboles measured at 985 K show a systematic deviation from ideal mixing consistent with a subregular solution model. The deviations from ideal mixing are interpreted in terms of Na ordering in the A-site and Na-Al interactions in edenite-poor compositions. Enthalpies of edenite substitution reactions in amphiboles and in SiO2-NaAlO2 glasses and framework silicates are comparable. Gibbs free energies of formation of fluortremolite and fluoredenite at 298K are -2,821.07±3.34 kcal mol–1 and -2,889.59±2.40 kcal mol–1 respectively. The former value is in good agreement with values calculated from both F-OH exchange experiments and from a natural fluortremolite-bearing metamorphic rock. Least-squares fitted sub-regular heat-of-mixing parameters are poorly constrained and unrealistically high, but estimated subregular mixing parameters consistent with 95% confidence interval uncertainties in the calorimetric data and with TEM constraints give activity-composition relations in good agreement with the A-site compositions of natural metamorphic and igneous hornblendes. These relations predict unmixing in edenite-rich compositions over a wide range of temperature, but lend no support to the existence of a hornblende-actinolite miscibility gap. Calibration of the reaction tremolite+ albite=edenite+4 quartz as a function ofP,T andX ed amph indicates negativedP/dT slopes and a limited range of X ed amph (0.3 to 0.5) in equilibrium with plagioclase and quartz over a wide range of pressure and temperature, consistent with metamorphic hornblende-plagioclase assemblages. The energetics of this reaction suggest, however, that amphibole-plagioclase disequilibrium may be common.  相似文献   

20.
In contrast to adjacent volcanic centers of the modern central Aleutian arc, Seguam Island developed on strongly extended arc crust. K-Ar dates indicate that mid-Pleistocene, late-Pleistocene, and Holocene eruptive phases constitute Seguam. This study focuses on the petrology of the mid-Pleistocene, 1.07–07 Ma, Turf Point Formation (TPF) which is dominated by an unusual suite of porphyritic basalt and basaltic andesite lavas with subordinate phenocryst-poor andesite to rhyodacite lavas. Increasing whole-rock FeO*/MgO from basalt to dacite, the anhydrous Plag+Ol+Cpx±Opx±Mt phenocryst assemblage, groundmass pigeonite, and the reaction Ol+Liq=Opx preserved in the mafic lavas indicate a tholeiitic affinity. Thermometry and comparison to published phase equilibria suggests that most TPF basalts crystallized Plag+Ol+Cpx±Mt at 1160°C between about 3–5 kb (±1–2% H2O), andesites crystallized Plag+Cpx+Opx±Mt at 1000°C between 3–4 kb with 3–5% H2O, and dacites crystallized Plag +Cpx±Opx±Mt at 1000°C between 1–2 kb with 2–3% H2O. All lavas crystallized at f o 2 close to the NNO buffer. Mineral compositions and textures indicate equilibrium crystallization of the evolved lavas; petrographic evidence of open-system mixing or assimilation is rare. MgO, CaO, Al2O3, Cr, Ni, and Sr abundances decrease and K2O, Na2O, Rb, Ba, Zr, and Pb increase with increasing SiO2 (50–71%). LREE enrichment [(Ce/Yb)n=1.7±0.2] characterizes most TPF lavas; total REE contents increase and Eu anomalies become more negative with increasing SiO2. Relative to other Aleutian volcanic centers, TPF basalts and basaltic andesites have lower K2O, Na2O, TiO2, Rb, Ba, Sr, Zr, Y, and LREE abundances. 87Sr/86Sr ratios (0.70361–0.70375) and ratios of 206Pb/204Pb (18.88–18.97), 207Pb/204Pb (15.58–15.62), 208Pb/204Pb (38.46–38.55) are the highest measured for any suite of lavas in the oceanic portion of the Aleutian arc. Conversely, Nd values (+5.8 to+6.7) are among the lowest from the Aleutians. Sr, Nd, and Pb ratios are virtually constant from basalt through rhyodacite, whereas detectable isotopic heterogenity is observed at most other Aleutian volcanic centers. Major and trace element, REE, and Sr, Nd, and Pb isotopic compositions are consistent with the basaltic andesitic, andesitic, dacitic, and rhyodacitic liquids evolving from TPF basaltic magma via closed-system fractional crystallization alone. Fractionation models suggest that removal of 80 wt% cumulate (61% Plag, 17% Cpx, 12% Opx, 7% Ol, and 3% Mt) can produce 20 wt% rhyodacitic residual liquid per unit mass of parental basaltic liquid. Petrologic and physical constraints favor segregation of small batches of basalt from a larger mid-crustal reservoir trapped below a low-density upper crustal lid. In these small magma batches, the degree of cooling, crystallization, and fractionation are functions of the initial mass of basaltic magma segregated, the thermal state of the upper crust, and the magnitude of extension. Tholeiitic magmas erupted at Seguam evolved by substantially different mechanisms than did calc-alkaline lavas erupted at the adjacent volcanic centers of Kanaga and Adak on unextended arc crust. These variable differentiation mechanisms and liquid lines of descent reflect contrasting thermal and mechanical conditions imposed by the different tectonic environments in which these centers grew. At Seguam, intra-arc extension promoted eruption of voluminous basalt and its differentiates, unmodified by interaction with lower crustal or upper mantle wallrocks.  相似文献   

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